Primary cell



R. W. REID PRIMARY CELL Nov. 4, 1952 Filed Dec. 22, 1949 y f@ ZM oa .MAM/m mm mdc .ww mi mae ooe o /r0/ @M anw Mm@ 4 @Md .m. www/,7., .4f/,

INVENTOR. Raymond/44 Re/'a/ ATTORNEYS Patentd Nov. 4, 1952 PRIMARY cELI.

Raymond W. Reid, Sanford, Mich., assignor 'to The Dow Chemical Company, Midland, Mich., a corporation of Delaware Application December 22, 1949, Serial No. 134,364

Yor the magnesium-base alloys as the anode material are increasing in importance because of the vavailability,` and abundance ofthe anode material and the higher voltage and capacity of the cells compared to conventional zinc dry cellsofrthe same size. The performance characteristics of the dry cells employing magnesium or magnesium-base alloy anodes withV various formulations of aqueous electrolytes are set forth in a paper by R. C. Kirk and A. B. Fry, Magnesium Dry Cells" which appeared in the Journal of the Electrochemical Society, vol. 94, No.

`6, Dec., 1948, pages 277 to 289, inclusive. In assembling these cells, the usual procedure is to form the anode material into a cup or battery can which constitutes one of the electrodes of the cell as well as the container holding the cathode elements and electrolyte. The cathode mix consists ofrmanganese dioxide having intimately mixed with it usually between about 5 and 15 per cent of linely-divided carbon, such as acetylene black, by weight. The mixture is moistened with enough electrolyte to make it moldable and the moldable mixture is formed nto"bobbins around a central Velectrode in the form of a rod of carbon or graphite. These bobbins are simply cylindrical moldings somewhat smaller than the battery can and are inserted into the cans after they are lined with starch paste of gelled electrolyte or a porous nonconductor, such as cloth or paper, to keep the bobbin from touchingthe can. In some instances, the cathode mix is introduced into the lined cans without previously forming the mix into a bobbin,

7 Claims. (Cl. 13G-V100) ing a manganese dioxide depolarized cathode. mix with a magnesium or magnesium alloy anode in assembling the aforesaid typeof dry or nonspillable'cell having an aqueous electrolyte, it is not necessary to preventV the cathode mix from touching the anode material. By allowing thecath.- ode mix to come into direct contact with the inside of the battery can, for example, I am thereby'enabled to eliminate the use of a porous liner or spacer material between the cathode mix and the magnesium or magnesium alloy anode. As a consequence of eliminating this feature of conventional dry cell construction, I have effected important economies of dry cell manufacture. In addition, there is obtained the surprising result of a marked increase in capacity or output of 'electrical energy compared to that of similar nection with the accompanying drawing in whichthe single figure is a diagrammatic verticalsection of a form of primary cell embodying the invention. A

As` shown,` the cell illustrated is contained in and comprises the can l formed of magnesium or magnesium-base alloy. i The can also serves as the anode of the cell and may be provided with a binding post 2. Placed directly in the can is the cathode mix 3 so that the mix isk in direct contact with Vthe inside of the can. A carbon or graphite rodv 4 is positioned centrally in the mix which is tamped around the rod so as to make `electrical contactA therewith. The lower end 5 of the rod is spaced apart fromA the inside` -V As to the electrolyte, there may be used any Y of the alkali or alkaline earth metal bromides,` preferably either magnesium bromide or stron` tium bromide, dissolved in water in amounts of from about grains per liter up to saturating amounts A generally` suitable concentration is between about 250 and 350 grams per liter. It is generally desirablefto include in solution in the electrolyte a small amount of a "soluble chromate'of anv alkali, alkali earth metal 0r ammonium. These chromates tend to reduce open circuit anode corrosion and thus prolong shelf life.

In assembling a cell, the cathode mix of manganese dioxide and finely-divided carbon may be moistened with the electrolyte in amount sufficient to render the mixture moldable and the moistened mixture molded into a cylindrical form or bobbin, around the central electrode, that will t into the battery can easily. If desired, the moistened mixture may be introduced into the can directly without first forming a mold or bobbin, leaving room for the central electrode 4 which may be inserted into the cathode mix after it is in the can. The cathodemix is then tamped tightly in the annular space between the central electrode and inside of the can so that the mix makes direct contact with both the can l and the electrode 9, thus in effect short circuiting the cell. After tamping the cathode mix into the can and around the electrode, a cardboard washer 9 is inserted and then molten sealing wax may be poured over the top of the washer toform the sealing cover II.

Although the cathode mix short circuits the cell, I have found, that this effect is only temporary and the cell quickly functions to produce a normal potential difference between its terminals that remains longer at a comparatively high value While discharging than similar cells in which the cathode mix is spaced apart from the insides of the can as in conventional cell construction.

As illustrative of the foregoing cell, the following is cited: A cell, No. 1, Was made in size D, the can being drawn from a magnesium-base alloy having the nominal composition of 3 per cent Al, 1 per cent Zn, 0.2 per cent Mn, the balance being magnesium. The cathode mix consisted of manganese dioxide 90 parts and acetylene black 10 parts, intimately mixed, The electrolyte was a water solution containing 300 grams of magnesium bromide (MgBrzI-IzO) Der liter and 10 grams of ammonium chromate per liter. The cathode mix was moistened with the electrolyte in the proportion `of 380 c. c. of electrolyte per 1000 grams of cathode mix. The can was charged with 50 grams of the moistened mix to Which an additional 7 grams of the electrolyte were added. A carbon electrode was pushed into the mix in the can Vand the mix tamped in place. A paper washer was `placed over and spaced from the top of the mix and the sealing Wax Was poured into the can over the washer to seal the cell. On being discharged continuously through a 7.5 ohm resistance 36 hours elapsed before the voltage dropped to 0.9. For comparison, a similar cell (No. 2) was made in which the cathode mix was of the same composition but separated from the can by a lining of starch paste as in conventional cell construction. On being continuously discharged through a resistance of 7.5 ohms only 19.5 hours elapsed before the voltage of the cell dropped to 0.9 volt.

Another cell, No. 3, made similarly to No. 1 showed a Voltage of 1.12 while discharging after continuously discharging for 24 hours through a 7.5 ohm resistance. After a rest period of 24 hours, the closed circuit ohms) voltage was 1.4 volts. After a further rest period of 16 days, the closed circuit (5 ohms) voltage was 1.4 volts.

Further examples of unlined cells of the invention in which the cathode mix was composed of manganese dioxide having about per cent by weight of acetylene black in admixture are set forth in the following table. In making up the cells, a standard D size can formed of a magnesium-base alloy was used and the cathode Inix was moistened with the electrolyte in the proportion of about 563 c. c. of electrolyte solution per 1000 grams of cathode mix.

moistened with said electrolyte and direct contact with the anode.

2. A primary cell according to claim 1 having a soluble chromate dissolved in aqueous solution of the electrolyte, said soluble chromate being selected from the group consisting of thealkali and alkali earth metal chromates and bichromates.

3. A primary cell according to claim 1 Yin which the bromide is magnesium bromide.

4. A primary cell according to claim 1 in which the bromide is strontium bromide.

5. A primary cell according to claim 1 in which the bromide is ammonium bromide.

6. A primary cell according to claim 1 in'which the bromide is lithium bromide.

7. A primary cell according to claim -1 inwhirch the bromide is sodium bromide.

RAYMOND W. REID.

REFERENCES CITED The following references are of record in the le of this patent:

UNITED STATES PATENTS Number Name Date 1,901,588 Eckstein Mar. v14, 1933 2,050,172 Gordon Aug. 4, 1936 2,116,091 Williams May 3, 1938 2,343,194 LawsonV Feb. 29, 1944 2,547,907 Fry Apr. 3, 1951 2,547,908 Fry Apr. B, 1951 OTHER REFERENCES Kirk et al., Magnesium -Dry- Cells, Journal of the Electro-Chemical Society, vol. .94, No. 6, December 1948, pages 277-289. 

1. A PRIMARY CELL HAVING AN ANODE FORMED OF MAGNESIUM OR A MAGNESIUM-BASE ALLOY, A CATHODE MIX OF MANGANESE DIOXIDE AND FINELY-DIVIDED CARBON, AND A ELECTROLYTE COMPRISING AN AQUEOUS SOLUTION OF A BROMIDE SELECTED FROM THE GROUP 